US2213988A - Lubricant - Google Patents

Description

Patented Sept. 10, 1940 LUBRICANT Bert H. Lincoln, Ponca City, Okla., and Alfred Henriksen, deceased, late of Ponca City, Okla, by John W. Wolfe, administrator de bonis non, Ponca City, Okla, assignors, by mesne assignments, to The Lnbri-Zol Development Corporation, Cleveland, Ohio, a corporation of Delaware I No Drawing. Application September 16, 1938,

I SerialNo. 230,339

17 Claims. (01.252-48) Our invention relates to lubricating oils and particularly to an oil having high pressure-sustaining film-forming qualities.

" N This application is a continuation in part of copending application Serial No. 687,682, filed August 31, 1933.

Hydrocarbon lubricating oils per se will not withstand high pressures imposed during thin film or non-viscous lubrication. Under pressure the film of oil will rupture. A metal to metal contact under comparatively low loads results. This weakness, inherent in the very best quality hydrocarbon lubricants, has prevented designers of mechanical equipment from making certain desirable changes which would greatly improve mechanical devices in general.

One object of our invention isto increase the load-carrying properties of hydrocarbon lubricants by imparting to them an increased film strength. Another object of this invention is to obtain such increased film strength without at the same time rendering the lubricating composition corrosive, especially to alloy bearing metals containing a characterizing proportion of cadmium, nickel, copper, lead, silver or tin and evento inhibit such corrosion by the lubricating oil base.

means hereinafter fully described and particularly pointed out in the claims, the following description setting forth in detail certain approved combinations of ingredients embodying my invention, such disclosed means constituting, however, but certain of various forms in which the principle of the invention may be used.

In general our invention comprises the addition of halogenated thioethers to hydrocarbon lubricants to obtain the desired film strength improvement.

It is believed that under conditions of extreme pressure the halogenated addition agents of this invention reac-tchemically or physlcochemically with the metallic surfaces to form a non-fiuxing surface which will not seize or score. This invention is not intended to be limited, however, by any particular theoryor explanation of the action upon the metallic surfaces.

All of the various halogens are effective when employed in accordance with the present invention but chlorine is generally. preferred inasmuch as it is the least expensive and one of the most effective of the halogens. Bromine and fluorine are more expensive and the latter is relatively difiicult to handle but they are each usable in accordance with this invention. Iodine is not so readily obtainable as the other halogens and is quite expensive but it also is satisfactory in providing effective addition agents. It should also be noted that two or more different halogens may be present in the same molecule. The brom-chlor and fiuorinated chlorine or bromine compounds give'especially satisfactory results.

Halogenation may continue until sumcient halogen to form the mono-chlor product has been added or'mixtures of less or greater halogen content may be employed. The halogen content of the halogenated thioether to be added to the lubricant may vary from about 5% to about The halogenated thioethers contemplated for use in accordance with our invention will be found to be particularly useful in that they combine the desirable characteristics of both sulphur and halogen in a single addition agent andv in such form that a cooperative result; not secured by any other type of addition agent, is attained. The outstanding characteristic of the halogenated thioethers which makes them particularly suitable as addition agents is their provision of generally higher film strength due to the combined presence of both sulphur and halogen in the oil, coupled with their corrosion inhibitor effect-on the surfaces being lubricated. Unusually high film strength combined with effectiveness'as a corrosion inhibitor is a characteristic not usually possessed by film strength addition agents. Specific examples of the halogenated thioethers which may be employed in attaining the above-named desirable ends are as follows:

- (A) Chlorinated aliphatic thioethers:

(1) Diohloro-di-ethyl sulfide (2) Chlorodi-n-butyl sulfide (3) Chlorodilauryl sulfide (4) Chloro-ethyl octadecyl sulfide (5) Chloro octadecyl butyl sulfide ethers:

p-Chloro-o-cresyl ethyl sulfide Chloroethyl' phenyl sulfide 4-chloronaphthyl lauryl sulfide (4) p-Nitro-o-chloro phenyl octadecyl sulfide (5) 2-hydroxynaphthyl-fl-chloroethyl sulfide (D) Chlorinated alicyclic thio-ethers:

(1) Monochloro cyclohexyl sulfide (2) Dichioro cyclohexyl sulfide (3) Tetrachloro cyclohexyl sulfide (4) Chloro cyclopentyl sulfide (5) Chloro cyclobutylsulfide (6) .Chloro methyl cyclohexyl sulfide (7) Sym-dichlor dipentyl cyclohexyl sulfide (8) Sym-dichlor dioctadecyl cyclohexyl sulfide (9) Chlor cyclohexyl phhyl thio-ether (10) Chloro cyclonexyl benzyl thio-ether (E) Chlorinated heterocyclic thio-ethers:

(1) Chloro furfuryl thio-ether (2) Chloro iurfuryl methyl thio-ether (3) Chloro furfuryl phenyl thio-ether (4) Chloro furfuryl cyclo hexyl thio-ether vention to provide the addition agents in the form of a concentrate in a suitable oil, said 011 containing rather high percentages of the addition agents. Such concentrates may be employed for future blending with alubricating oil in the proportions desired for the particular conditions of use.

When used in conjunction with a mineral lubricating oil it is obvious that generally only such amounts of the addition agent may be included as are soluble in the specified amount of oil. By the term soluble" as herein used it is intended to indicate the ability to form not only true solutions but also any form of substantially permanently homogeneous composition when incorporated in mineral oil. With most of the compounds there is usually little difliculty, especially if the incorporation is effected in the manner described in Cornell Patent No. 2,042,880,

and since quite small percentages often give remarkably improved results it is seldom of extre'me importance that the addition agents be oil-soluble in all proportions.

The halogenated thioethers are quite eflfective when used in relatively small amounts as addition agents to lubricating compositions. This invention contemplates the use of from about 0.1% or even less to about 20% by weight, based on the amount of oil, of these addition agents and for the crankcase of internal combustion engines amounts from about 0.1% to about 2% are often suflicient. In the case of gear lubricants larger quantities, from about 2% to about 10%, may often be preferred. 1 However, under certain relatively unusual circumstances where the thickfilm and other properties of the ordinary mineral lubricating oil are not required to any great de- (0) Chlorinated mixed aromatic-aliphatic thiogree the addition agent of this invention may be employed as the major component of the lubrieating composition, only such proportion of lu-' bricating oil being present as may be required to afiord the characteristics desired.

Since,' in general, the loss of the addition agent by volatilization will be less for compounds having a low volatility, the vapor pressure of the compounds should, for most purposes, be less than atmospheric pressure at temperatures up to 140 C. It is often desirable, especially for use in internal combustion engines, that the vapor pressure be less than atmospheric at temperatures up to 170 C. In the case of compounds which are stable at temperatures up to their boiling points, this condition may be expressed by stating that the boiling point'of the compound should, in general, be higher than 140 C., and for certain uses, such as internal combustion engines, higher than 170 C.

While the lubricating compositions which have been described herein as illustratin one embodiment of the invention have been generally referred to as oils, 1. e., liquids, this invention is, however, also applicable to the solid and semisolid types of lubricants commonly referred to in the trade as greases, bodied oils, etc.

The compounds of this invention are highly eflective when employed as addition agents to lubricants for internal combustion engines such as airplane and Diesel engines. The halogenated thioethers are especially desirable for such uses inasmuch as both sulphur and halogen are found included in the same molecule thus affording a very effective composition which is nevertheless safe and non-corrosive under diificult operating conditions.

While mineral oil generally is the principal ingredient of the lubricating composition, it is not essential that it be the only ingredient other than the addition agent, provided that there be no additional ingredient which is incompatible with such addition agent. It is within the contemplation of this invention to include, if necessary or desirable, such other addition agents as are commonly added to improve the viscosity index or cold test of the lubricant and a lubricating composition according to this invention which also has a separate oiliness-increasing agent has been found to be especially effective.

Other modes of applying the principle of our invention may be employed instead of the one explained, change being made as regards the composition and method herein disclosed, provided the ingredients or steps stated by any .of the following claims or the equivalent of such stated ingredients or steps be employed.

We, therefore, particularly point out and distinctly claim as our invention:

1. A lubricating composition comprising a major proportion of mineral oil and a halogenated thio-ether.

2. A lubricant comprising in combination a major proportion of an oil of lubricating viscosity and a halogenated thio ether.

3. A lubricating composition comprising a major proportion of mineral oil and a minor amount of a halogenated thio-ether.

4. A lubricating composition 0 mprising a major proportion of mineral oil a from about cm. to about 20%, by weight based on the to about 10%, by weight, based on the amount oi mineral oil, oi a halogenated thin-ether.

6. A lubricating composition comprising a major proportion of mineral oil and irom about 0.1% to about 2%, by weight, based on the amount oi mineral oil, oi a halogenated thio-ether.

7. A lubricating composition comprising a major proportion oi mineral oil and a minor amount oi a halogenated thio-ether having a vapor pressure less than atmospheric at 140 C.

8. A lubricating composition comprising a major proportion oi mineral oil and irom about 0.1% to about 20%, by weight, based on the amount oi mineral oil, oi a halogenated thio-ether having a vapor pressure less than atmospheric at 140 C.

9. A lubricating composition comprising a major proportion oi mineral oil and irom about 0.1% to about 10%, by weight, based on the amount or mineral oil, oi a halogenated thio-ether, havinga vapor pressure less than atmospheric at 140 C.

10. A lubricating composition comprising a ma- :Ior proportion oi mineral oil and from about 0.1%

to about 2%, by weight, based on the amount oi mineral oil. of a halogenated thio-ether having a vapor pressure less than atmospheric at 140 C.

11. A lubricating composition comprising a major proportion oi mineral oil and a minor amount oi a halogenated thio-ether having a vapor pressure less than atmospheric at 1'70 C. p 12. A lubricating composition comprising a maior proportion oi mineral oil and irom about 0.1

to about 20%, by weight, based on the amount oi mineral oil,- oi a halogenated aliphatic thin-ether havirog a vapor pressure less than atmospheric at 1 C. J

ummmmr de m 13. A lubricating composition comprising a major proportion oi mineral oil and irom about 0.1% to about 20%, by weight, based on the amount oi mineral oil, oi a halogenated aromatic thio-ether lligving a vapor pressure less than atmospheric at 14. A lubricating composition comprising a major proportion oi mineral oil and from about 0.1%. to about 20%, by weight, based on the amount of mineral oil, oi a halogenated alicyclic thio-ether llizg'ing a vapor pressure less than atmospheric at C.

15. A lubricating composition comprising a ma- Jor proportion oi mineral oil and irom about 0.1% to about 20%, by weight, based on the amount oi mineral oil, oi a halogenated cyclic this-ether having a vapor pressure less than atmospheric at 140 C.

16. A lubricating composition comprising a ma-' ior proportion oi mineral oil and irom about 4% to about 20%, byweight, based on the amount oi mineral oil, oi a-halogenated cyclo-aliphatic thio- BERT H. LINCOLN. JOHN W. WOLFE,

V non of the. Estate of Alfred Hem-Ibsen, Deceased.